Sulfated oil soluble phenol formaldehyde polymers



3,049,511 Patented Aug. 14, 1962 No Drawing. Filed June 15, 1959, Ser.No. 820,108 9 Claims. (Cl. 260-49) This invention, in general, relatesto new compositions of matter and their use in the treatment ofemulsions of mlneral oils and Water, such as petroleum emulsionscommonly encountered in the production, handling and re" fining of crudemineral oil. This application is a contmuation-in-part of our copendingapplication Serial No. 632,433, filed January 4, 1957.

Petroleum emulsions are, in general, of the water-in-oil type whereinoil is the continuous phase and the discon tinuous or dispersed phasecomprises finely-divided particles of naturally occurring waters orbrines. These emulsions are often extremely stable and will not resolveinto the oil and water components even on long standing. The emulsionsobtained from producing Wells and from the bottom of crude oil storagetanks are commonly referred to as cut oil, emulsified oil, bottomsettlings and BS. It is also to be understood that water-in-oilemulsions may occur artificially, resulting from any one or more ofnumerous operations encountered in various industries.

One type of process involves subjecting emulsions of the water-in-oiltype to the action of a deemulsifying agent of the kind hereinafterdescribed, thereby causing the emulsion to resolve and stratify into itscomponent parts of oil and water or brine after emulsion has beenallowed to stand in a relatively quiescent state.

One object of our invention is to provide novel and economical eifectivecompositions for resolving emulsions of the character referred to intotheir component parts of oil and water or brine.

Another object is to provide novel reagents which are surface-active inorder to enable their use as deemulsifiers or for such uses Wheresurface-active characteristics are necessary or desirable. Other objectswill appear hereinafter.

In accordance with the invention, the crude oil deemulsifying agents arethe sulfation products of oxyalkylated alkyl phenol-formaldehyde resins.The phenol-formaldehyde resins are the alkali-insoluble reactionproducts of formaldehyde with a difunctional, monoalkyl phenol, thealkyl group having between 4-15 carbons, inclusive, preferably 5-15carbons. Dialkyl, monofunctional phenols are not suitable forcompositions of this invention, but amounts up to dialkyl phenol in themonoalkyl phenol reactant may be tolerated. The Weight ratio of theoxyalkylene groups, e. g., oxyethylene or both oxyethylene andOxypropylene groups, to the phenol-formaldehyde condensation productwill, for most applications, fall between about 1:2 and 15:1,respectively, preferably the range of 1:2 to 9:1. Where mixtures ofethylene oxide and 1,2- propylene oxide are used to oxyalkylate thephenol-formaldehyde condensation product they may be reacted as amixture or the oxides be added sequentially-one oxide being added to theresin first and the other oxide being added to the oxyalkylene groups.Ordinarily, we prefer to oxyalkylate with propylene oxide first.

In this manner the terminal oxyalkylation groups are those ofoxyethylene, which have primary hydroxyl groups. Oxypropylene groups, onthe other hand, have terminal secondary hydroxyl groups, which are moredifficult to sulfate. Simultaneous reaction of a mixture of the oxidesprobably gives an oxyalkylated product having both types of terminalhydroxyl groups. When the ethylone oxide and propylene oxide are mixedprior to oxyalkylation, the preferred Weight ratio of the two oxides isin the range of 1:4 to 4:1. When these oxides are reacted in sequentialfashion, the weight ratio of oxyethylene to Oxypropylene groups is about4:1 to 1:25, respectively.

PHENOL-FORMALDEHYDE CONDENSATION The phenol-formaldehyde condensationproducts are prepared by reacting formaldehyde or a substance whichbreaks down to formaldehyde under the reaction conditions, e.g.,paraformaldehyde and trioxane, and a difunctional, monoalkyl phenol, byheating the reactants in the presence of a small amount of an acidcatalyst such as sulfamic acid under substantially anhydrous conditionsexcepting the water produced during the reaction. The aqueous distillatewhich begins to form is collected and removed from the reaction mixture.After several hours of heating at temperatures slightly above theboiling point of water, the mass becomes viscous and is permitted tocool to about to C. At this point a suitable hydrocarbon fraction isadded, and heating is resumed. Further aqueous distillate begins to formand heating is continued for an additional number of hours until atleast about one mol of aqueous distillate per mol of reactants has beensecured. The product is permitted to cool to yield thephenol-formaldehyde condensation product in a hydrocarbon solvent. Themolecular weight of these intermediate condensation products cannot beascertained with certainty, but we would approximate that the resinsemployed herein should contain about 4 to 15, preferably 4 to 10,phenolic nuclei per resin molecule. The solubility of the condensationproduct in hydrocarbon solvent would indicate that the resin is a lineartype polymer, thus distinguishing them from the more commonphenol-formaldehyde resins of the cross-linked type.

The alkyl phenols should have the alkyl group in the orthoorpara-position so that the phenolic reactant has difunctionality. Thealkyl group must have at least 4, preferably at least 5, carbon atomswith about 15 carbon atoms being the maximum. Such phenols includep-tertiary butyl phenol, p-amyl phenol, p-tertiary hexyl phenol,p-n-hexyl phenol, p-octyl phenol, p-nonyl phenol, pdodecyl phenol,mixtures thereof, and mixtures of such monalkyl phenols with not morethan 25 by Weight of monofunctional, dialkyl phenols such as acommercial grade crude alkylate phenol consisting of about 90% p-nonylphenol and 10% dinonyl phenol.

This aspect of the invention is illustrated in the following examplesbut is not limited thereto. The parts are by weight.

Example A In a three-necked reaction flask provided with means ofmechanical stirring and a return condenser system permitting the removalof any aqueous phase formed in the course of reaction, there is added1500 parts of a crude alkylate phenol which comprises about 90% p-nonylphenol and approximately 10% of dinonylphenol, 225 partsparaformaldehyde and 3 parts sulfamic acid which is present as acatalyst in the reaction. The reaction mass is heated, and at 108 C. anaqueous distillate begins to form. After three hours heating atapproximately 110 C. the mass becomes quite viscous and is permitted tocool to about 100 C. At this point, 600 parts of a suitable hydrocarbonfraction such as S0 extract is added, and heating is resumed. Again at100 C. further aqueous distillate begins to form, and heating iscontinued for an additional three hours to a maximum temperature of 212C. The product is permitted to cool to yield the finishedphenol-formaldehyde resin in the hydrocarbon solvent.

Example B In a manner similar to Example A, 1000 parts of the crudealkylate phenol, 120 parts of paraformaldehyde and 2 parts sulfamic acidwere heated 2 hours at 105110 C. to permit reaction of the phenol andformaldehyde under conditions minimizing formaldehyde loss. Attemperatures above 110 C. vigorous reaction sets in which must becontrolled by cooling. After about 27 parts of aqueous distillate havebeen secured, the reaction comes under control and becomes exceedinglyviscous. At this point the resin is cooled to 105 C., and 400 parts of asuitable hydrocarbon fraction such as S extract is added. Heating iscontinued for an additional three hours, or until a total of about 75parts of aqueous distillate have been removed at maximum temperature of212 C. to yield the finished phenol-formaldehyde resin in thehydrocarbon solvent.

Example C In a manner similar to Examples A and B, 1000 parts of thecrude alkylate phenol, 90 parts paraformaldehyde and 2 parts sulfamicacid are carefully reacted at temperatures of 100110 C. When thereaction mass becomes quite viscous, it is permitted to cool, and 400parts of S0 extract are added. Heating is resumed for an additionalhour, or until a total of 55 parts of aqueous distillate have beensecured at maximum temperature of 210 C. to yield the finishedphenol-formaldehyde resin in the hydrocarbon solvent.

Example D In a manner similar to Example A, 1200 parts of ptertiarybutyl phenol, 275 parts of paraformaldehyde and 3 parts of sulfamic acidare heated slowly. An aqueous distillate begins to form at about 105110C. After 3 hours of heating at 105110 C. with the removal of the aqueousdistillate, the reaction mass is cooled to about 100 C. Then 600 partsof S0 extract is mixed with the reaction mass, and heating is resumed.At about 100 C., further aqueous distillate comes off and heating iscontinued for an additional three hours to a maximum final temperatureof 205210 C. The mass is then cooled to room temperature.

Example E The procedure of Example D is repeated with the substitutionof an equivalent amount of p-hexyl phenol for the p-tertiary butylphenol.

In the preceding examples, sulfamic acid has been used as the acidcatalyst to assist in the condensation reaction. Other suitableequivalent acids which may be used in place of sulfamic acid are mineralacids such as sulfuric acid, hydrochloric acid, phosphoric acid, etc.

As stated heretofore, intermediate phenol-formaldehyde resin shouldcontain a minimum of about 4 phenolic nuclei and should not exceed aboutphenolic nuclei. It is extremely difiicult, if not impossible, toaccurately determine the molecular weight of the intermediate resinproducts. However, it is believed that the resin of Example A containsabout 10 phenolic nuclei per resin molecule, Example B, about 7 phenolicnuclei, and Example C, about 4 phenolic nuclei per resin molecule.

OXYALKYLATION OF THE CONDENSATION PRODUCTS Having prepared theintermediate phenol-formaldehyde products, the next step is theoxyalkylation of the condensation products with the alkylene oxideshaving 2-3 carbons. This is achieved by mixing the intermediatephenol-formaldehyde condensation product in a hydrocarbon solvent with asmall amount of a suitable catalyst in an autoclave. The condensationproduct is heated above 100 C., and ethylene oxide or a mixture ofethylene oxide and propylene oxide, either as a mixture of by sequentialaddition of first either the propylene oxide or the ethylene oxide andlater the other oxide, is charged into the autoclave until the pressureis in the vicinity of 75100 p.s.i.

The reaction mixture is gradually heated until an exothermic reactionbegins. The external heating is then removed, and alkylene oxide isadded at such a rate that the temperature is maintained between aboutISO-160 C. in a pressure range of to p.s.i. After all of the alkyleneoxide has been added, the temperature is main tained for an additional10 to 20 minutes to assure substant-ially complete reaction of thealkylene oxide. The resulting product is the alkylene oxide adduct of analkyl phenol-formaldehyde condensation product, in which the weightratio of the oxide to the condensation product is between about 1:2 and15:1, respectively, preferably 1:2 to 9: 1. The molecular weight of theoxyalkylated phenolformaldehyde condensation products of this inventionrange from as low as about 1100 to as high as about 50,000.

Some preferred embodiments of the oxyalkylated, alkylphenol-formaldehyde condensation products and methods of theirpreparation are illustrated in the following examples wherein all partsare by weight unless otherwise stated, but the invention is not limitedthereto.

Example F In an autoclave having a two-liter capacity equipped with ameans of external electric heating, internal cooling coils andmechanical agitation, there is charged 950 parts of the resin solutionof Example A, and 1.5 parts of sodium hydroxide. Into a transfer bombthere is introduced 575 parts ethylene oxide. The resin is heated to C.,and the ethylene oxide is charged into the reactor until reactorpressure is 80 p.s.i. The reaction mixture is gradually heated until anexothermic reaction begins to take place. The external heating is thenremoved and ethylene oxide is then added at such a rate that thetemperature is maintained between -160 C. with a pressure range of 80 to100 p.s.i. After approximately two hours all of the oxide has been addedto the autoclave, and the temperature is maintained for an additional 15minutes to make certain that the unreacted oxide is reduced to aminimum. The resulting product is the ethylene oxide adduct of aphenol-formaldehyde resin, in which the weight ratio of oxide to resinby weight is 2 to 3. The oxyalkylated phenol-formaldehyde condensationproduct had a hydroxyl equivalent weight of about 620 and con tainedabout ten oxyalkylene chains per resin molecule.

Example G In a manner similar to Example F, the ethylene oxide adduct ofthe resin of Example B was prepared in which the ratio of ethylene oxideto resin was 1% to 1 by weight. The oxyalkylated phenol-formaldehydecondensation product had a hydroxyl equivalent weight of about 840 andcontained about four oxyalkylene chains per resin molecule.

Example H In the same facilities as used in Example F, there is charged172 parts of the resin solution of Example A and 1 part of sodiumhydroxide. Into a transfer bomb there is introduced 250 parts by weightof ethylene oxide and 250 parts of propylene oxide. The intermediate isheated to 135 C., and the mixed oxides are charged into the reactoruntil the reactor pressure is 80 p.s.i. The reaction conditions fromhereon are identical with those employed in Example D. The resultingproduct is the mixed oxide adduct of a phenol-formaldehyde resin inwhich the ratio of oxide to resin by weight is approximately 4 to 1. Theoxyalkylated. phenol-formaldehyde condensation product had a hydroxylequivalent weight of about 1400 and contained about ten oxyalkylenechains per resin molecule.

Example J In a manner similar to Example H, using a 1 to 1 by weightratio of ethylene oxide and propylene oxide, a

mixed oxide adduct of the resin of Example C was prepared in which theratio of oxide to resin was 6 to 1. The oxyalkylated phenol-formaldehydecondensation product had a hydroxyl equivalent weight of about 1400 andcontained about four oxyalkylene chains per resin molecule.

Example K In a manner similar to Example H using a 1 to 3 by weightratio of ethylene oxide to the propylene oxide, a mixed oxide adduct ofthe resin of Example C was prepared in which the ratio of oxide to resinwas 6 to 1. The oxyalkylated phenol-formaldehyde condensation producthad a hydroxyl equivalent weight of about 1500 and contained about fouroxyalkylene chains per resin molecule.

Example L In a manner similar to Example H using a 1 to 3 by weightratio of ethylene oxide to propylene oxide, a mixed oxide adduct of theresin of Example B was prepared in which the ratio of oxide to resin was2 to 1.

Example M In a manner similar to Example H using a 3 to l by weightratio of ethylene oxide to propylene oxide, a mixed oxide adduct of theresin of Example A was prepared in which the ratio of oxide to resin was1 to 1. The oxyalkylated phenol-formaldehyde condensation product had ahydroxyl equivalent weight of about 700 and contained about tenoxyalkylene chains per resin molecule.

Example N In a manner similar to Example F there is prepared a propyleneoxide adduct of the resin of Example A in which the ratio of propyleneoxide to resin by weight is 1 to 1. The oxypropylatedphenol-formaldehyde resin was then reacted further with ethylene oxideuntil the finished product contained 10% by weight of ethylene oxide.The oxyalkylated phenol-formaldehyde condensation product had a hydroxylequivalent weight of about 750 and contained about ten oxyalkylenechains per resin molecule.

Example Example P In a manner similar to Example N a propylene oxideadduct of the resin of Example A was prepared in which the ratio ofpropylene oxide to resin was 9 to 1 by weight. This oxypropylatedphenol-formaldehyde resin was then further reacted with ethylene oxideuntil the finished material contained by weight of ethylene oxide. Theoxyalkylated phenol-formaldehyde condensation product had a hydroxylequivalent weight of about 1400 and contained about ten oxyalkylenechains per resin molecule.

Example Q In a manner similar to Example N a propylene oxide adduct ofthe resin of Example C was prepared in which the ratio of propyleneoxide to resin was 2 to 1 by weight. This oxypropylatedphenol-formaldehyde resin was then further reacted with ethylene oxideuntil the finished material contained 30% by weight of ethylene oxide.The oxyalkylated phenol-formaldehyde condensation product had a hydroxylequivalent weight of about 1200 and contained about four oxyalkylenechains per resin molecule.

Example R Into the gas charge vessel of an oxyalkylation unit is charged250 parts of ethylene oxide and 250 parts of propylene oxide. The gasesare circulated via a circulating pump to mix them thoroughly. Then 2,000parts of the phenol-formaldehyde resin solution of Example D and 3.8parts of sodium hydroxide are charged into the oxyalkylation. Thereactor is purged with natural gas. The mixed oxides are added at 150160C. The oxyalkylation is completed at this temperature and a pressure of100 p.s.i. The gases are recycled in the unit for two hours after theaddition of oxides is complete. The resulting product is oxyalkylationproduct of the phenolformaldehyde resin wherein the oxyethylene andoxypropylene groups are mixed heterogeneously in the oxyalkylene adductradicals.

Example S In a manner similar to Example R, 7200 parts of the resinsolution of Example D and 1800 parts of an ethylene oxide-propyleneoxide mixture (2 parts by weight propylene oxide per part ethyleneoxide) are reacted in the presence of 13 parts of sodium hydroxide.

Example T The mixed oxyethylene and oxypropylene adduct of thephenol-formaldehyde resin of Example E is prepared by substituting theresin solution of Example E for the resin solution of Example D in theprocedure of Example S.

SULFATION OF THE OXYALKYLATED CON- DENSATION PRODUCTS The next and finalstep in the preparation of the compositions of our invention is thesulfation of the oxyalkylated alkyl phenol-formaldehyde condensationproducts. The degree of sulfation may range from compositions in whichonly one hydroxyl group per oxyalkylated phenol-formaldehyde resinmolecule is sulfated to total sulfation of the hydroxyl groups of theoxyalkylated resin. The preferred sulfating reagent is sulfamic acidbecause of the ease and convenience in handling in plant operations. Thesulfo groups, however, can be introduced by other means such as sulfuricacid, sulfur trioxide, etc. With the use of these latter reagents it isessential that the temperature conditions of reaction be lower and becarefully controlled so that the sulfation reaction proceeds Withoutdecomposition of the oxyalkylated phenol-formaldehyde resin. Other thanthe careful control of temperature conditions and sulfation at lowertemperatures, the reaction conditions employed for the preparation ofthe sulfo derivatives with the lastmentioned sulfating agents aresubstantially identical to those for sulfation with sulfamic acid. Thesulfation is accomplished by heating and stirring a mixture of theoxyalkylated phenol-formaldehyde resin and the sulfating reagent. Themixture is heated in the vicinity of about 120-150 C. in the case ofsulfamic acid and held at that point for approximately two hours underagitation to complete the sulfation reaction. The sulfated product soprepared is then cooled below about C., at which point a suitablehydrocarbon extract is added to yield a solution of the finishedproduct. It has been observed that increasing the number of lsulfogroups per molecule results in substantially increased viscosity of thesulfated product.

The sulfated oxyalkylated resin may be used in the acid form or anysuitable form wherein the ionizable hydrogen is replaced by a metal orother suitable cation. In many instances, it is desirable that thecompositions be in the form of salts of alkali metals or the ammoniumsalt. These salts may be obtained by reacting the acidic product with ametallic hydroxide, ammonia, or an organic base, or an alkaline salt ofone of these. Suitable bases and salts include ammonium, sodium andpotas sium hydroxides and carbonates, as :well as bicarbonates; aqueousammonia; and amines such as lower alkyl amines, lower alkanol amines,and simple aryl amines.

7 Sulfamic acid as the sulfating reagent yields the ammonium salt.

The following examples will further illustrate the nature of thecompositions of this invention in preferred embodiments thereof, but theinvention is not limited to these examples.

Example I In a three-necked reaction flask provided with means ofmechanical stirring and heating there is added 200 parts by Weight of amaterial as prepared in Example L and 2. parts by weight of sulfamicacid. The mixture is heated to 130 C. and held at that point for twohours to complete the sulfation reaction. The reaction product soprepared is cooled to below 100 C. at which point 175 parts by weight ofa suitable hydrocarbon extract such as S extract is added to yield thefinished product. This sulfation reaction results in the introduction ofapproximately one rsulfato group per oxyalkylated resin molecule.

Example 11 Example III In a manner similar to Example I, 200 parts ofthe oxyalkylated resin of Example G was reacted with 32 parts by weightof sulfamic acid to yield a partially sulfated oxyalkylatedphenol-formaldehyde resin in which approximately one-half of the freehydroxyl groups of the resin were sulfated. To this sulfated productthere was added 175 parts by weight of a suitable hydrocarbon fractionsuch as S0 extract to yield the finished product. It is believed thatthere is about two free hydroxyl groups remaining per molecule in thisproduct.

Example IV In a manner similar to Example I, 200 parts by weight of theoxyalkylated resin of Example R is reacted with parts by Weight ofsulfamic acid at l130 C. for

two hours. To the cooled reaction product is added 175 parts by weightof S0 extract.

Example V In a manner similar to Example I, 200' parts by Weight of theoxyalkylated resin of Example T is reacted with 8 parts by weight ofsulfamic acid at 125-130 C. for two hours. To the cooled reactionproduct is added 175 parts by weight of S0 extract.

Among the suitable hydrocarbon vehicles which can be employed assolvents for our sulfated resins is sulfur dioxide extract. Thismaterial is a byproduct from. the Edeleanu process of refining petroleumin which the undesirable fractions are removed by extraction with liquidsulfur dioxide. After removal of the sulfur dioxide a mixture ofhydrocarbons, substantially aromatic in character, remains and isdesignated in the trade as sulfur dioxide extract or SO extract.Examples of other suitable hydrocarbon vehicles are toluene, xylene, gasoil, diesel fuel, bunker fuel and coal tar solvents. The above citedexamples of solvents are adaptable to azeotropic distillation as wouldalso be any other solvent which is immiscible with water, miscible withthe reacting mass and has a boiling point or boiling range in excess ofthe boiling point of water.

8 DEEMULSlFICATiON The compositions of this invention are surface-activeand are particularly suitable for the deemulsification of crude oilemulsions. Deemulsification is achieved by mixing the deemulsifyingagents of this invention, at a ratio in the approximate range of onepart of the deemulsifying agent to 2,00050,000 parts of the emulsion,and thereafter allowing the emulsion to remain in a relatively quiescentstate during which separation of the oil and water occurs. Thedeemulsifying agents of this invention may be used in conjunction withother deemulsifying agents from classes such as the petroleum sulfonatetype, of which naphthalene sulfonic acid is an exarnpie, the modifiedfatty acid type, the amine modified oxyalkylated phenol-formaldehydetype, and others.

The effectiveness of the compositions of this invention as deemulsifyingagents is illustrated in the following tests and data.

BOTTLE TESTING OF CRUDE OIL EMULSION S The bottle testing of crude oilemulsions is conducted according to the following procedure: Freshsamples of the emulsion-breaking chemicals in organic solvent solutionare prepared in 10% solutions. These solutions are made by accuratelydiluting l0 milliliters of the emulsionbreaking chemicals in millilitersof a mixture of equal parts of anhydrous isopropyl alcohol and anaromatic hydrocarbon such as xylene. The mixture is agitated well untilthe emulsion-breaking chemical is completely dissolved.

The equipment for running the crude oil emulsionbreaking test, inaddition to the fore o'ing 10% solutions, includes a set of six ouncegraduated prescription bottles, a funnel, a graduated 0.2 milliliterpipette, a thief pipette, a centrifuge, centrifuge tubes and athermometer. The graduated prescription bottles are filled to themilliliter mark with the crude oil emulsion to be tested, preferably asample which has been recently collected. If there is any free water inthe crude oil emulsion sample collected, it is bled olf before thebottles are filled. Each bottle is inverted several times with the thumbover the opening of each bottle so that the bottle will be coated withan emulsion film.

By means of the 0.2 milliliter pipette, the prescribed volume of the 10%solution of the emulsion-breaking chemical is added to the emulsion inthe bottles. The bottles are then capped and given manual agitation fora predetermined number of counts. The number of counts are determined bya survey of the agitation which can be secured in the system in whichthe crude oil emulsion is being used. If the emulsion requires heat fortreatment, the bottles are placed in hot water bath, the length of timeand temperature determined by the particular plant equipment andpractice in which the particular emulsion is employed. If the plantprovides for hot agitation of the emulsion the bottles may be given acorresponding amount of manual hot agitation.

The bottles are then removed from the hot water bath and the water drop,presence of the bottom settlings (B.S.) layer and color and generalappearance of the oil are noted.

A thief grind-out is taken on all bottles which appear to be promising.A thief grind-out is made by preparing centrifuge tubes filled withgasoline to the 50% mark. The thief pipette is set to the proper lengthby adjusting the rubber stopper so that the bottom of the pipette isabout inch above the oil-water level of the bottle with maximum waterdrop. This same setting is used for all subsequent thiefings onremaining bottles. The thiefed oil from each bottle is added to thecentrifuge tube to the 100% mark, and the tube is shaken. The samplesare then centrifuged for three minutes.

With certain paraflin base oils a portion of the parafiin is thrown downwith the 13.8. If the centrifuge tubes are heated to 150 F. the parafiinwill melt and be dissolved in the gasoline-oil mixture and usually willnot be thrown down again with the BS. upon centrifuging while hot.However, occasionally the paratfin will re-congeal as the tube coolsduring centrifuging. If this occurs, the tube is removed from thecentrifuge and heated to 150 F. without shaking or disturbing thesettled B.S. layer. The heated sample is then centrifuged for seconds.This should give a true B.S. reading free of paraffin.

An excess chemical grind-out is then run on each can trifuge by addingseveral drops of -a solution in white gasoline or other solvent of achemical which causes complete separation of the water and oil. Withsome sensitive emulsions the chemical Will cause reemulsification. Inthese instances it is necessary to rethief and add a lesser amount. Eachtube is vigorously shaken to make sure that the packed B.S. layer isbroken up and the tubes heated to 150 F. in the case of troublesomeparaihn base crude oil. The samples are then centrifuged for threeminutes.

During the test the speed of the water drop is observed carefully afterthe emulsion-breaking chemical is added to the prescription bottles. Theobservation of the color and brilliance of the oil in transmitted lightis very important. In general, the brilliance and depth of colorincreases with a decrease in 13.5. & W. (bottom settlings and Water)content. The observations of color are made in the oil in theprescription bottle before and after heat treatment. In the idealtreatment of crude oil emulsions the oil-water line could be a sharp,clean line without any Web or sludge present. Presence of a considerableamount of sludge or web is undesirable because this foreign materialwill eventually go to stock in the treating plant and be reported asB.S. Traces of web or sludge, however, will disappear or be removed inthe normal treating plant,

In almost all instances the thief grind-out and excess chemicalgrind-out readings indicate the formula that has most nearly producedcrude oil free from B3. and water. The most efficient emulsion-breakingchemical is determined by the foregoing test procedure by the overallconsideration of the following factors: relative speed of the breakingof the emulsion which is usually indicated by speed of water drop, colorand brilliance of the oil layer, the relative absence of web or sludgeat oil-water line and the ability to most nearly produce treated oilthat is free from E5. and water.

By way of illustrating the effectiveness of the emulsionbreakingchemicals contemplated by this invention, the composition of Example Iwas tested according to the foregoing bottle testing procedure onsamples of 28 gravity crude oil obtained from Spivey Field, Kansas. Thecrude oil emulsion contained about 56% water. The commercial treatingchemical being used on the lease and the treating chemical of Example Iwere both tested for comparative purposes. These treating chemicals wereadded at a ratio of 0.06 part of a 10% solution, as described in theforegoing procedure, to 100 parts of the emulsion fluid. The sampleswere given 150 shakes cold and 50 shakes hot, the hot temperature being170' E. The observations made during the tests were recorded and aresummarized in the following table.

Similar tests were made on a crude oil emulsion containing about 64%water of a gravity crude oil from TABLE II Thief Excess Water DropGrind-Out Grind-0ut Treating Chemical 15 min. 60 min. B.S. Water B.S.Water Commercial Chemal 7 15 31.0 34. 0 O 56.0 Example I 25 62 2. 4 00 1. 2

The invention is hereby claimed as follows:

1. The oil soluble product of the reaction of sulfamic acid with anoxyalkylated oil soluble, alkali insoluble, linear polymer offormaldehyde and an alkyl phenol which is at least 75% mono-alkyldifunctional phenol wherein the alkyl group has 4 to 15 carbon atoms,the oxyalkylene groups contain 2 to 3 carbon atoms, and the weight ratioof said oxyalkylene groups to said alkyl phenol-formaldehyde polymer isin the range of 1:2 to 15: 1, said alkyl phenol-formaldehyde polymercontaining 4 to 15 phenolic nuclei, the quantity of sulfarnic acid beingsufiicient to introduce into said oxyalkylated alkyl phenol-formaldehydepolymer at least one sulfate group in the form of the ammonium salt.

2. The product as claimed in claim 1 in which the weight ratio of saidoxyalkylene groups to said alkyl phenol-formaldehyde polymer is in therange of 2:3 to 9:1.

3. The product as claimed in claim 1 in which not exceedingapproximately one-half of the free hydroxyl groups in the alkylphenol-formaldehyde polymer are sulfated with sulfamic acid.

4. The product as claimed in claim 1 in which approximately one hydroxylgroup in the oxyalkylated alkyl phenol-formaldehyde polymer is sulfatedwith sulfamic acid.

5. The product as claimed in claim 1 in which substantially all of thefree hydroxyl groups in the oxyalkylated alkyl phenol-formaldehydepolymer are sulfated with sulfamic acid.

6. The product as claimed in claim 1 in which the oxyalkylene groups aresolely oxyethylene groups.

7. The product as claimed in claim 1 in which the oxyalkylene groups aresolely oxypropylene groups.

8. The product as claimed in claim 1 in which the oxyalkylene groups aremixed oxyethylene and oxy-1,2-propylene groups in a weight ratio withinthe range of 1:4 to 4:1.

9. The product as claimed in claim 1 in which oxypropylene groups arefirst added to the alkyl phenol-formaldehyde polymer followed byoxyethylene groups and the weight ratio of oxyethylene to oxypropyleneis within the range of 4:1 to 1:25.

References Cited in the file of this patent UNITED STATES PATENTS2,454,542 Bock et al. Nov. 23, 1948 2,454,543 Bock et al. Nov. 23, 19482,560,741 Provost et a1 July 17, 1951 2,854,428 De Groote Sept. 30, 1958OTHER REFERENCES The Condensed Chemical Dictionary, 5th Ed., Chapman &Hall (1956), page 39, under alkali.

1. THE OIL SOLUBLE PRODUCT OF THE REACTION OF SULFAMIC ACID WITH ANOXYALKLATED OIL SOLUBLE, ALKALI INSOLUBLE, LINEAR POLYMER OFFORMALDEHYDE AND AN ALKYL PHENOL WHICH IS AT LEAST 75% MONO-ALKYLDIFUNCTION PHENOL WHEREIN THE ALKYL GROUP HAS 4 TO 15 CARBON ATOMS, THEOXYALKYLENE GROUPS CONTAIN 2 TO 3 CARBON ATOMS, AND THE WEIGHT RATIO OFSAID OXYALKYLENE GROUPS TO SAID ALKYL PHENOL-FORMALDEHYDE POLYMER IS INTHE RANGE OF 1:2 TO 15:1, SAID ALKYL PHENOL-FORMALDENHYDE POLYMERCONTAINING 4 TO 15 PHENOLIC NUCLEI, THE QUANTITY OF SULFAMIC ACID BEINGSUFFICIENT TO INTRODUCE INTO SAID OXYALKYLATED ALKYLPHENOL-FORMALDEHYDRE POLYMER AT LEAST ONE SULFATE GROUP IN THE FORM OFTHE AMMONIUM SALT.